JP2952336B2 - Method for producing organic germanium compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing an organic germanium compound. Organic germanium compounds are used as additives to catalysts and polymers, and are attracting attention as fungicides, preservatives, antitumor agents and the like. In addition, it has been spotlighted as a monomer for producing a germanium-containing polymer useful as an electronic and optical functional material.

[0002]

2. Description of the Related Art Conventionally, organogermanium compounds have been produced by reacting halogermanes with carbanion reagents such as Grignard reagents and organolithium reagents, or by reacting germyl anions with organic halides. However, these methods use a highly reactive anion reagent, and thus have a problem in industrial use. In addition, halogermanes generate a germyl anion by a metal exchange reaction with a Grignard reagent or the like, so that a side reaction also occurs. Furthermore, these methods are not suitable for the production of compounds having a halogen-germanium bond, since the bond reacts with the reaction reagent under the reaction conditions.

[0003] Another method for producing organogermanium reagents is the hydrogelmylation reaction of hydrogermanes with acetylenes or olefins. This method can also produce a compound having a halogen-germanium bond, but this method cannot be applied in principle when an organic group newly introduced on germanium is not derived from acetylenes or olefins.

[0004]

In order to overcome these problems of the prior art, it is necessary to provide a new method for bonding an organic group and germanium without using an anion reagent. , A novel organogermanium compound is provided.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that alkyl, alkenyl, aryl or aralkyl halides are
The present inventors have found a novel fact that they easily react with polyhalodigermanes in the presence of a palladium-containing catalyst, and have completed the present invention based on this finding.

That is, according to the present invention,(1) General formula X-R¹−X (V) (where R¹Is an alkylene group which may have a substituent,
Alkenylene group, arylene group, aralkylene group or 2
X is a valent heterocyclic group, and X represents a halogen atom. )so
An organic halogen compound represented by a palladium-containing catalyst
In the presence of the general formula Z_mA¹ _nA² _3-mnGeGeA¹ _nA² _3-mnZ_m (II) (wherein Z represents a chlorine or bromine atom;¹And A
²Represents an alkyl group, a cycloalkyl group, an aryl group,
Represents a alkyl group or a fluorine atom, m and n are 1 or
Is 2. React with digermanes represented by)
A general formula Z_mA¹ _nA² _3-mnGeR¹GeA¹ _nA² _3-mnZ_m (VI) (wherein, R¹, Z, A¹, A², M and n are the same as above
Meaningful. ) And the organic germanium compound represented by
And / or general formula X_mA¹ _nA² _3-mnGeR¹GeA¹ _nA² _3-mnZ_m  (VII) (wherein, R¹, X, Z, A¹, A², M and n are as described above.
Has the same meaning. The organic germanium compound represented by)
Object and / or general formula X_mA¹ _nA² _3-mnGeR¹GeA¹nA² _3-mnX_m  (VIII) (wherein, R¹, X, A¹, A², M and n are the same as above
Meaningful. ) Of the organic germanium compound represented by
A manufacturing method is provided.

In the organic halogen compound represented by the general formula XR ¹ -X (V) used in the present invention, the divalent organic group R ¹ is an alkylene group, an alkenylene group, an arylene group,
Various aralkylene groups or divalent heterocyclic groups are used. Examples thereof include 1,3-dibromopropane, 1,2-dichloroethylene, 1,2-dibromoethylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 2,5-dibromothiophene, and benzal chloride. ,
Benzal bromide, α, α′-dichloro-p-xylene and the like can be mentioned.

[0008] digermane compound represented by is another raw material used in the present invention the general formula ^{_{Z m A 1 n A 2 3}} -m-n GeGeA 1 n A 2 3-m-n Z m (II) is Various substituents having a chlorine or bromine atom as the substituent Z and an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a fluorine atom as A ¹ and A ² are used. -Dichloro-1,1,2,2-tetramethyldigermane, 1,2-dichloro-1,1,2,2-tetraethyldigermane, 1,1,2,2-tetrachloro-
1,2-diphenyldigermane, 1,2-dibromo-
1,2-dimethyl-1,2-dicyclohexyl digermane and the like can be mentioned.

The ratio of the organic halide to the digerman compound used in the present invention is not particularly limited.
In consideration of the yield and the like, the range is preferably about 100 to 1/10.

In the present invention, a palladium-containing catalyst is used as a catalyst. As the palladium-containing catalyst, various known catalysts can be used, and a catalyst supported on activated carbon or the like, a salt, a complex having a ligand, or the like can be used. Specific examples thereof include palladium carbon, palladium acetate, palladium chloride, dichlorobis (triphenylphosphine) palladium, dichlorobis (triethylphosphine) palladium, dichlorobis (trimethylphosphine) palladium, dichlorobis (trimethylphosphite) palladium, and tetrakis (trikis). Examples thereof include (phenylphosphine) palladium, tetrakis (triethylphosphine) palladium, tris (triphenylphosphite) palladium, dichlorobis (benzonitrile) palladium, and bis (dibenzylideneacetone) palladium. These supported catalysts, salts, complexes, etc. can be used alone, but phosphines such as triphenylphosphine, methyldiphenylphosphine, trimethylphosphine, triethylphosphine, etc., in an amount of about 1 to 10 times the palladium atom, In the presence of a phosphite such as phosphite, triphenyl phosphite, 1-phospha-2,6,7-trioxa-4-ethylbicyclo [2,2,2] octane or a ligand such as isonitrile May be used.

The amount of the palladium-containing catalyst used may be a so-called catalytic amount, and is generally used in a molar ratio to digermanes in the range of 0.00001 to 0.5.
The reaction of the present invention is carried out at 0 ° C. or higher,
Carried out at a reaction temperature of Further, the reaction of the present invention can be carried out in the presence or absence of a solvent, but when a solvent is used, a commonly used solvent, for example, various organic solvents such as benzene, toluene, and hexane are used. be able to. Separation and purification of the desired product from the reaction mixture can be easily achieved by means generally used in organic chemistry such as distillation and chromatography.

The general formula Z obtained by the present invention_mA¹ _nA² _3-mnGeR¹GeA¹ _nA² _3-mnZ_m (VI) X_mA¹ _nA² _3-mnGeR¹GeA¹ _nA² _3-mnZ_m  (VII) X_mA¹ _nA² _3-mnGeR¹GeA¹ _nA² _3-mnX_m  The organic germanium compound represented by (VIII) includes a substituent
R¹Represents an alkylene group, alkenylene group, aryle
Group, an aralkylene group or a divalent heterocyclic group,
¹And A²Are an alkyl group, a cycloalkyl group,
A reel group, an aralkyl group or fluorine as a substituent Z
Represents a chlorine or bromine atom;
There are obtained a variety of compounds having a nitrogen atom. These organic
As an example of a rumanium compound, 1,3-bis (chloro
Dimethylgermyl) propane, 1,2-bis (chlorodi
Methylgermyl) ethylene, 1,2-bis (bromodim
Chillgermil) ethylene, 1,4-bis (chlorodimethyi)
Lugermyl) benzene, 1,4-bis (bromodimethyl)
Gelmyl) benzene, 1-bromodimethylgermyl-2
-Chlorodimethylgermylbenzene, 1-iododimethy
Lugermyl-2-chlorodimethylgermylbenzene,
2,5-bis (chlorodimethylgermyl) thiophene,
2-bromodimethylgermyl-5-chlorodimethylgel
Milthiophene, 2,5-bis (bromodimethylgermi
L) thiophene, α, α'-bis (chlorodimethyl gel)
Mill) toluene, α, α'-bis (chlorodimethyl gel)
Mill) -p-xylene and the like.

[0013]

According to the present invention, various organic germanium compounds can be obtained from various organic halogen compounds without using an anionic reagent. In particular, even when an organic group newly introduced on germanium is not derived from acetylene or olefin, an organic germanium compound having a halogen-germanium bond can be easily produced, and its industrial value is large.

[0014]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 In an autoclave, 1,2-dichloro-1,1,2,2-
1 mmol of tetramethyldigermane, 0.05 mmol of tetrakis (triphenylphosphine) palladium, t
trans-1,2-dichloroethylene 0.5 mmol,
2 ml of toluene was added, and the mixture was heated and stirred in an oil solution at 180 ° C for 15 hours. After cooling in the autoclave, as a result of gas chromatography analysis, trans-1,2-bis (chlorodimethylgermyl) ethylene was produced in an amount of 0.30 mmol.

Example 2 ci-1, instead of trans-1,2-dichloroethylene
A reaction was carried out in the same manner as in Example 1 except that s-1,2-dichloroethylene was used. As a result, trans-1,2-bis (chlorodimethylgermyl) ethylene 0.08 mmol
1 was generated.

EXAMPLE 3 Instead of trans-1,2-dichloroethylene, p-
The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at 150 ° C. for 20 hours using dibromobenzene. As a result, 0.06 mmol of p-bis (chlorodimethylgermyl) benzene was obtained.
1 was obtained.

Example 4 α, instead of trans-1,2-dichloroethylene
0.50 mmol of α'-dichloro-p-xylene and 2 ml of benzene in place of toluene were used.
The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out for a time.
0.30 mmol of -p-xylene was obtained. The reaction solution was subjected to Kugelrohr distillation to isolate 0.24 mmol. This is a new compound not listed in the literature, and its spectroscopic data is as follows.

Α, α′-bis (chlorodimethylgermyl) -p-xylene: bp 125 ° C./6 mmHg (Kuger lower) mp 80-82 ° C .; ¹ HNMR (CDC
l ₃ ) δ 0.61 (s, 12H, GeCH ₃ ), 2.6
3 (s, 4H, ArCH ₂ Ge), 6.99 (s, 4
_{H, C 6 H 4);} MS (EI) m / s ( relative intensity) 38
0 (M ⁺ , 12), 243 (M ⁺ -GeMe ₂ Cl, 5
4) 139 (GeMe ₂ Cl, 100); Elemental analysis found: C, 37.22; H, 5.04, C ₁₂ H ₂₀ C.
calculated for _{l 2 Ge 2: C, 37.89} , H, 5.
29.

Example 5 Instead of trans-1,2-dichloroethylene,
Using 1.00 mmol of 5-dibromothiophene,
Reaction was carried out in the same manner as in Example 1 except that the amount of -dichloro-1,1,2,2-tetramethyldigermane was 4.00 mmol, and 2 ml of benzene was used in place of toluene and reacted at 150 ° C. for 12 hours. As a result, a mixture of 2,5-bis (chlorodimethylgermyl) thiophene, 2-bromodimethylgermyl-5-chlorodimethylgermylthiophene, and 2,5-bis (bromodimethylgermyl) thiophene was obtained. . After treating the reaction solution with methyl lithium, Kugelrohr distillation was performed to obtain 0.56 mmol of 2,5-bis (trimethylgermyl) thiophene. Each product is a novel compound not listed in the literature, and its spectroscopic data is as follows.

2,5-bis (chlorodimethylgermyl)
Thiophene; MS (E / I) m / s (relative intensity) 358
(M ⁺ , 21), 343 (M ⁺ -Me, 100), 13
_{9 (GeMe 2 Cl, 39)} . 2,5-bis (trimethylgermyl) thiophene: bp 100 ° C./6 mmHg
(Kugel lower); ¹ H NMR (acetone-d ₆ ) δ
0.33 (s, 18H, GeCH ₃ ), 7.17 (s,
2H, = CHCH =): MS (EI) m / z (relative intensity) 318 (M ⁺ , 9), 303 (M ⁺ -Me, 10)
0), 119 (Me ₃ Ge, 17); high resolution MS 3
_19.9666, calculated for _{C 10 H 20 Ge 2 S;} 319.9705.

Example 6 A reaction was carried out in the same manner as in Example 5 , except that 1 mmol of 1,4-jodobenzene was used instead of 2,5-dibromothiophene, the reaction temperature was 120 ° C., and the reaction time was 10 hours. Methylated. By Kugelrohr distillation, 1,
4-bis (trimethylgermyl) benzene 0.51 mm
ol was obtained.

Continuation of front page (56) References JP-A-48-67223 (JP, A) JP-A-52-83334 (JP, A) JP-A-52-111549 (JP, A) JP-A-56-122389 (JP, A) , A) JP-A-57-146787 (JP, A) Qrganometal. Chem. , 117 [3] (1976), C55-C57 Qrganometallics, 6 [5] (1987), 974-979. Qrganometal. Chem. , 148 [1] (1978), 97-106.

Claims (1)

(57) [Claims] 1. A compound of the general formula XR¹−X (V) (where R¹Is an alkylene group which may have a substituent,
Alkenylene group, arylene group, aralkylene group or 2
X is a valent heterocyclic group, and X represents a halogen atom. )so
An organic halogen compound represented by a palladium-containing catalyst
In the presence of the general formula Z_mA¹ _nA² _3-mnGeGeA¹ _nA² _3-mnZ_m (II) (wherein Z represents a chlorine or bromine atom;¹And A
²Represents an alkyl group, a cycloalkyl group, an aryl group,
Represents a alkyl group or a fluorine atom, m and n are 1 or
Is 2. React with digermanes represented by)
A general formula Z_mA¹ _nA² _3-mnGeR¹GeA¹ _nA² _3-mnZ_m (VI) (wherein, R¹, Z, A¹, A², M and n are the same as above
Meaningful. ) And the organic germanium compound represented by
And / or general formula X_mA¹ _nA² _3-mnGeR¹GeA¹ _nA² _3-mnZ_m  (VII) (wherein, R¹, X, Z, A¹, A², M and n are as described above.
Has the same meaning. The organic germanium compound represented by)
Object and / or general formula X_mA¹ _nA² _3-mnGeR¹GeA¹nA² _3-mnX_m  (VIII) (wherein, R¹, X, A¹, A², M and n are the same as above
Meaningful. ) Of the organic germanium compound represented by
Production method.